CN105121496A - Toughened epoxy thermosets containing core shell rubbers and polyols - Google Patents

Toughened epoxy thermosets containing core shell rubbers and polyols Download PDF

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Publication number
CN105121496A
CN105121496A CN201380074212.8A CN201380074212A CN105121496A CN 105121496 A CN105121496 A CN 105121496A CN 201380074212 A CN201380074212 A CN 201380074212A CN 105121496 A CN105121496 A CN 105121496A
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China
Prior art keywords
curable resin
weight
resin composition
epoxy resin
anhydride
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Inventor
S·B·克拉默
R·谢
G·古利亚斯
M·J·马克斯
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Blue Cube Intellectual Property Co Ltd
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Blue Cube Intellectual Property Co Ltd
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Publication of CN105121496A publication Critical patent/CN105121496A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D121/00—Coating compositions based on unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J121/00—Adhesives based on unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Paints Or Removers (AREA)

Abstract

A curable resin composition comprising: a) an epoxy resin; b) an anhydride hardener; c) a polyol; d) a core shell rubber, and (e) a catalyst, is disclosed. When cured, the resin composition can be used to formulate composites, coatings, laminates, and adhesives.

Description

Malleableize epoxy resin thermosetting thing containing core shell rubbers and polyvalent alcohol
Technical field
The present invention relates to malleableize composition epoxy resin; And more particularly, the present invention relates to polyvalent alcohol and the purposes of core shell rubbers (CSR) tough agent in composition epoxy resin.
Background technology
There are the various currently known methodss using multiple obtainable known tough agent (such as CSR or polyvalent alcohol) malleableize epoxy resin-acid anhydrides thermosetting thing.In epoxy preparation, use CSR to be that preparation viscosity significantly improves as the main weak point of tough agent.Compared with CSR, the preparation viscosity that polyvalent alcohol provides improves less, but it does not provide the fracture toughness property of same degree to improve, but also to glass transition temperature (T g) there is limited deleterious effect (if there is).
Therefore need to provide a kind of curable epoxy preparation with tough agent, described tough agent improves the snappiness of preparation, elongation and toughness and that preparation viscosity is improved is minimum, and can not reduce the T of the final thermosetting thing be made up of described epoxy preparation product gmaybe can not have injurious effects to it.
Summary of the invention
The present invention relates to the polyvalent alcohol of certain total amount and ratio and core shell rubbers (CSR) tough agent for malleableize epoxy resin-acid anhydrides preparation, and do not damage the machinery of thermosetting thing and thermal property and the purposes of good workability aspect is provided.
Advantageously, in curable epoxy preparation, use polyvalent alcohol and core shell rubbers (CSR) tough agent to be provided for the low viscosity of improved treatment, and there is the thermoset products of improvement snappiness and elongation and do not sacrifice the final T of gained thermosetting thing g.
One embodiment of the present of invention relate to a kind of curable resin composition or system (or preparation), comprise following each, are made up of or form primarily of following each following each: (a) at least one epoxy resin; (b) at least one anhydride curing agent; (c) at least one polyvalent alcohol; (d) at least one core shell rubbers (CSR); And (e) at least one curing catalysts.
Embodiment
epoxy resin
Curable compositions of the present invention comprises at least one epoxy resin, component (a).Epoxy resin can be saturated or unsaturated, aliphatic series, cyclic aliphatic, aromatic series or heterocycle, and can be and be substituted.Epoxy resin can also be monomer or polymerization.Be applicable to much epoxy resin of the present invention and see Lee, H. (Lee, and Neville H.), K. (Neville, K.) " epoxy resin handbook (HandbookofEpoxyResins) " McGraw-Hill Book Co (McGraw-HillBookCompany), New York (NewYork), 1967,2nd chapter, 257-307 page; Be incorporated herein by reference.
Epoxy resin for instant component (a) in embodiment disclosed in this article can change, and comprises known and commercially available epoxy resin, and it can use separately or with two or more array configuration.In the epoxy resin selecting the composition be used for disclosed by this paper, not only should consider the characteristic of final product, but also viscosity and other characteristic that may affect resin combination processing should be considered.
What skilled work personnel were known is especially applicable to the reaction product of epoxy resin based on polyfunctional alcohol, phenol, cycloaliphatic carboxylic acid, aromatic amine or amino-phenol and Epicholorohydrin.Some non-limiting examples comprise the triglycidyl ether of such as bisphenol A diglycidyl ether, Bisphenol F diglycidylether, resorcinol diglycidyl ether and p-aminophenol.Known other the applicable epoxy resin of skilled work personnel comprise Epicholorohydrin respectively with ortho-cresol and the reaction product with phenolic aldehyde.Other epoxy resin comprises the epoxide of Vinylstyrene or divinyl naphthalene.Equally likely use the mixture of two or more epoxy resin.
Be applicable to the epoxy resin (component (a)) preparing curable compositions of the present invention, can select by commercially available product; Such as can purchased from Dow Chemical (TheDowChemicalCompany) .331, D.E.R.332, D.E.R.383, D.E.R.334, D.E.R.580, D.E.N.431, D.E.N.438, D.E.R.736 or D.E.R.732 epoxy resin or the Syna21 cycloaliphatic epoxy resin purchased from Si Nasiya (Synasia).As explanation of the present invention, epoxy resin ingredient (a) can be the mixture of liquid epoxies, such as D.E.R.383, epoxy novolac DEN438, cycloaliphatic epoxide Syna21 and diethylene dioxide base aromatic hydrocarbons, diethylene dioxide base benzene (DVBDO) with and composition thereof.
In certain embodiments, epoxy resin composition, by curable compositions gross weight (comprising epoxy resin, anhydride curing agent, polyvalent alcohol, CSR and catalyzer), can be present in curable compositions by the amount in curable compositions about 10 % by weight to about 90 % by weight scope.In other embodiments, composition epoxy resin can in curable compositions about 20 % by weight to about 80 % by weight scope; In other embodiments; In about 30 % by weight to about 70 % by weight scopes.
anhydride curing agent
Be applicable to the solidifying agent (also referred to as stiffening agent or linking agent) (component (b)) of curable epoxy resin composition of the present invention, cyclic aliphatic and/or aromatic series acid anhydride can be comprised; With and composition thereof.
Cyclic aliphatic acid anhydride stiffening agent especially can comprise such as methylnadic anhydride (nadicmethylanhydride), hexahydrophthalic anhydride, Tetra Hydro Phthalic Anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and its derivative; With and composition thereof.Aromatic series acid anhydride can comprise such as Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride with and composition thereof.Anhydride curing agent can also comprise multipolymer and the such as United States Patent (USP) the 6th of vinylbenzene and MALEIC ANHYDRIDE, 613, No. 839 and epoxy resin chemistry and technology (EpoxyResinsChemistryandTechnology), C.A. plum (C.A.May), Y. Tanaka (Y.Tanaka) compile, Marcel De Ke company limited (MarcelDekkerInc.) 1973 New York, other acid anhydrides described in 273-280 page (being incorporated herein by reference).
In certain embodiments, the mixture of anhydride hardener or anhydride hardener presses the total weight of epoxy resin composition, anhydride hardener, polyvalent alcohol, CSR and catalyzer, can be present in curable compositions by the amount in curable compositions about 10 % by weight to about 90 % by weight scope.In other embodiments, anhydride hardener generally can in curable compositions about 20 % by weight to about 80 % by weight scope; In about 30 % by weight to about 70 % by weight scopes; In about 30 % by weight to about 50 % by weight scopes.
polyvalent alcohol
In general, polyol component (component (C)) comprises number molecular-weight average and is greater than about 2,000 to about 20,000, in another embodiment about 3,000 to about 15,000 and in another embodiment about 4,000 to about 10, the polyvalent alcohol of 000 or the mixture of polyvalent alcohol.
The average functionality of polyol component is in 1.5 to 6.0 scopes.In another embodiment, the average functionality of polyol component is in 2 to 4 scopes.
The example of polyol component includes, but is not limited to polyether glycol, and such as polyoxytrimethylene, polyoxybutylene, polyoxyethylene and polytetramethylene ether diol, can be used as polyvalent alcohol is purchased from Dow Chemical, conduct glycol is purchased from Archie chemical company (ArchChemicalCompany), conduct purchased from English Weida (Invista) and purchased from Beyer Co., Ltd (BayerCorporation) polyvalent alcohol; Polyester polyol, such as poly-hexanodioic acid second diester, poly-hexanodioic acid fourth diester, poly-hexanodioic acid propylene diester, poly-hexanodioic acid second diester propylene diester, poly-hexanodioic acid second diester fourth diester etc., its mixture and multipolymer, can be used as polyester polyol is purchased from Chemtura (Chemtura) and conduct polyester polyol is purchased from Dow Chemical; Polycaprolactone polyol, such as, purchased from Bai Situo's (Perstorp) caprolactone polyol and purchased from Daicel (Daicel) caprolactone polyol; Polycarbonate polyol, such as, purchased from the OxymerM112 of Bai Situo; Hydroxy-end capped polyhutadiene, such as, purchased from Sartomer (SARTOMER) ; And the mixture of the said products and multipolymer.
In certain embodiments, polyvalent alcohol can be present in curable compositions by the amount in about 1 % by weight to about 30 % by weight scopes.In other embodiments, polyvalent alcohol can by about 1 % by weight to about 20 % by weight scopes; In about 5 % by weight to about 25 % by weight scopes; In other embodiments in about 2 % by weight to about 15 % by weight scopes; And the amount in other embodiments in about 3 % by weight to about 10 % by weight scopes exists, wherein above-mentioned scope is the total weight by epoxy resin composition, anhydride hardener, polyvalent alcohol, CSR and catalyzer.
CSR
Rubber particles core and outer shell is comprised for core shell rubbers of the present invention (component (d)).Core shell rubbers generally has at 0.01 μm to the particle diameter within the scope of 0.8 μm.In another embodiment, the particle diameter of core shell rubbers at 0.05 μm within the scope of 0.5 μm, and in another embodiment, at 0.08 μm within the scope of 0.30 μm.
Core shell rubbers is the polymkeric substance comprising rubber particles core, optionally middle layer and outer shell, described rubber particles core is by comprising elasticity or the rubber polymer polymer formation as main component, described middle layer is formed by the monomer with two or more double bonds and on core layers coated, and described outer shell is by the polymer formation of graft polymerization on the core.Outer shell is by partially or completely covering the surface of rubber particles core to core by monomer graft polymerizes.
In general, rubber particles core is made up of acrylic or methacrylic acid ester monomer or diene (conjugated diolefine) monomer or vinyl monomer or siloxane-type monomers and its combination.
Outer shell provides the consistency with preparation, and has limited swelling property so that CSR particle mixes and dispersion in resin of the present invention or stiffening agent.In one embodiment, shell does not have the reactive group about epoxy resin of the present invention or stiffening agent.In another embodiment, shell may have the reactive group about epoxy resin or stiffening agent, such as epoxy group(ing) or carboxylic acid group.
Be applicable to the CSR for the preparation of curable compositions of the present invention (component (d)) and commercially available product can be selected from; Such as, Palau moral (Paraloid) EXL2650A, EXL2655, EXL2691A, respectively can purchased from Dow Chemical; Or Zhong Yuan Co., Ltd. (KanekaCorporation) mX series, such as MX120, MX125, MX130, MX136, MX551; Or purchased from the large Boulogne SX-006 (METABLENSX-006) of U.S. of the beautiful sun of Mitsubishi (MitsubishiRayon).
In general, CSR component (component (d)) can be present in curable compositions by the amount in about 1 % by weight to about 25 % by weight scopes.In other embodiments, CSR can by about 2 % by weight to about 20 % by weight scopes; The amount of about 3 % by weight to about 15 % by weight exists in other embodiments; Wherein above-mentioned scope presses the total weight of epoxy resin composition, anhydride hardener, polyvalent alcohol, CSR and catalyzer.
The present invention uses two kinds of tough agents of difference, i.e. polyvalent alcohol and CSR.The relative quantity of tough agent and total amount for the minimal viscosity of combination obtaining acid anhydrides, CSR and polyvalent alcohol, and reach maximum flexibility and elongation but T to the cured epoxy resin thermosetting thing using the present invention to prepare gnot there is harmful effect most important yet.In general, in curable compositions, the minimum weight ratio of CSR and polyvalent alcohol can in about 0.1 to about 2 scopes, such as, in about 0.5 to about 2 scopes.In curable compositions, the maximum weight ratio of CSR and polyvalent alcohol can in about 2 to about 15 scopes, such as, in about 2 to about 7 scopes.In general, in curable compositions, the combination minimum of polyvalent alcohol and CSR can in 2 % by weight to about 10 % by weight scopes, such as, in 3 % by weight to about 5 % by weight scopes.In curable compositions, the combination maximum of polyvalent alcohol and CSR can in 8 % by weight to about 30 % by weight scopes, such as, in 10 % by weight to about 20 % by weight scopes.In certain embodiments, compared with independent acid anhydrides, the minimum percent of the acid anhydrides of combination, CSR and polyvalent alcohol medium viscosity improves can in about 50 to about 500 scopes, such as, in about 100 to about 500 scopes.
catalyzer
The catalyst component (e) of composition epoxy resin of the present invention is the compound for promoting preparation to solidify, and can comprise such as at least one tertiary amine, comprises the tertiary amine that phenol replaces; At least one boric acid-amine complex; At least one boron trifluoride-amine complex; At least one imidazoles or the imidazoles be substituted; At least one metal acetyl acetonates (such as Z. open (Z.Zhang), C.P. king (C.P.Wong) metal acetyl acetonates to the research (StudyontheCatalyticBehaviorofMetalAcetylacetonatesforEpo xyCuringReactions) of the catalysis behavior that epoxy resin cure reacts, journal of applied (JournalofAppliedPolymerScience), 86th volume, described in 1572-1579 (2002)); At least one transition metal (such as cobalt, nickel, zinc, chromium, iron, copper) salt; At least one quaternary ammonium Huo phosphonium salt; At least one phosphuret-(t)ed hydrogen or the phosphine compound be substituted; Or its combination.A large amount of catalyzer or accelerator are described in such as epoxy resin chemistry and technology, and C.A. plum, Y. Tanaka compile, and Marcel De Ke company limited 1973 New York, in 273-280 page (being incorporated herein by reference).
In certain embodiments, catalyzer can be present in curable compositions by the amount in 0 % by weight to about 10 % by weight or about 0.01 % by weight to about 7 % by weight scopes.In other embodiments, catalyzer can by about 0.1 % by weight to about 6 % by weight scopes, in other embodiments; Amount in about 0.5 % by weight to about 5 % by weight scopes exists; Wherein above-mentioned scope presses the total weight of epoxy resin composition, anhydride hardener, polyvalent alcohol, CSR and catalyzer.The reaction of epoxy resin and anhydride curing agent can be slowly, or can not occur outside above-mentioned catalyst concn scope.
optional component
Of the present invention curable or optionally can be applicable to other additive of its desired use containing one or more by thermoset composition.For example, the optional additives being applicable to the present composition can include, but is not limited to non-reactive diluent, stablizer, tensio-active agent, flow ability modifying agent, pigment or dyestuff, delustering agent, air release agent, fire retardant (such as inorganic combustion inhibitor, halogenated fire-retardants and non-halogenated flame retardent, such as phosphorated material), curing initiator, curing inhibitors, wetting agent, tinting material or pigment, thermoplastics, processing aid, UV blocking compound, fluorescent chemicals, UV stablizer, inert filler, fiber strengthening thing, antioxidant, comprise the anti-impact modifier of thermoplastic particles, with and composition thereof.Above-mentioned inventory intends to be exemplary and nonrestrictive.Preferable additives for preparation of the present invention can be optimized by those of skill in the art.
In certain embodiments, curable compositions presses curable compositions total weight, can also comprise 0 % by weight to about 70 % by weight optional additives; And in other embodiments, about 0.1 % by weight to about 50 % by weight optional additives.In other embodiments, curable compositions can comprise about 0.1 % by weight to about 10 % by weight optional additives; And in other embodiments, about 0.5 % by weight to about 5 % by weight optional additives.
for the manufacture of the method for composition
In one embodiment of the invention, disclose a kind of method for the preparation of composition referred to above, comprise two steps, be made up of two steps or form primarily of two steps.First step is distributed to by core shell rubbers in epoxy component or hardener component or polyol component.Second step is the epoxy resin of mixed C SR dispersion liquid and appropriate amount, anhydride hardener, polyvalent alcohol and catalyzer.
In one embodiment, first step, namely in discrete areas, under dispersion condition, CSR dispersion liquid is prepared with high-shear mixer, wherein said discrete areas is not containing solvent, and wherein said dispersion condition comprises the dispersion temperature of 40 DEG C to 100 DEG C, is greater than the Reynolds number (ReynoldsNumber) of 10 and the jitter time of 30 minutes to 300 minutes.
In one embodiment, super mixer is equipped with the modification of variable-speed controller, temperature probe and Kao Leisi mixing blade (cowlesmixingblade) or Kao Leisi.In order to realize best mixing resultant, the diameter of Kao Leisi mixing blade (D) generally between 0.2 to 0.7 of container (T) diameter (D/T=0.2 ~ 0.7), in another embodiment between 0.25 to 0.50, and in another embodiment between 0.3 to 0.4.The gap of blade and container bottom is generally 0.2D to 2.0D, is 0.4D to 1.5D in another embodiment, and is 0.5D to 1.0D in another embodiment.The height (H) of mixture is general between 1.0D to 2.5D, in another embodiment between 1.25D to 2.0D, and in another embodiment between 1.5D to 1.8D.Dispersion liquid region generally has at 0 DEG C to the dispersion temperature within the scope of 100 DEG C.In another embodiment, discrete areas has at 25 DEG C to the dispersion temperature within the scope of 90 DEG C, and has in another embodiment at 60 DEG C to the dispersion temperature within the scope of 80 DEG C.
Reynolds number is measuring of the ratio of mass force and viscous force.In general, discrete areas maintenance Reynolds number is greater than 10.In another embodiment, discrete areas maintains Reynolds number and is greater than 100, and maintenance Reynolds number is greater than 300 in another embodiment.
Discrete areas maintains to reach and realizes uniform, single/discrete particle and disperse the required time under dispersion condition.In one embodiment, discrete areas maintains 30 minutes to the time within the scope of 300 minutes under dispersion condition.In one embodiment, vacuum can be applied to remove any air retained.
In one embodiment, the dispersion liquid formed by this method contains 5 % by weight to 45 % by weight polymer particles.In another embodiment, the dispersion liquid of formation contains 10 % by weight to 40 % by weight polymer particles, and in another embodiment containing 25 % by weight to 30 % by weight polymer particles.
The second step preparing curable epoxy resin composition of the present invention is by mixing above-mentioned reactive component to realize.For example, can epoxy resin, solidifying agent, polyvalent alcohol, CSR dispersion liquid and catalyzer be added in mixing vessel; And by mixing, component is mixed with composition epoxy resin subsequently.To mixture order without critical condition, namely the component of preparation of the present invention or composition can by any order mixing to provide curable compositions of the present invention.
During mixing or mixing before, any one (such as the weighting agent) in various preparation additives optionally mentioned above can also be added in composition to form curable compositions.
Usually all components of composition epoxy resin is made can to prepare mixing at the temperature had for low viscous effective composition epoxy resin of required application and dispersion.In other embodiments, the temperature during mixing all components generally can at about 0 DEG C to about 100 DEG C, and preferred at about 20 DEG C to about 50 DEG C.
curable compositions
Curable compositions can as described above, by combination (1) aromatic epoxy resin or cycloaliphatic epoxy resin or cycloaliphatic epoxy resin, aromatic epoxy resin cycloaliphatic resin, epoxy phenolics, epoxy bisphenol A phenolic resin, polyfunctional epoxy resin, formed with (2) anhydride hardener, (3) polyvalent alcohol, (4) CSR and (5) catalyzer based on the mixture of the epoxy resin of dihydroxyphenyl propane or Bisphenol F.In addition, other additive can also be added as described above.The relative proportion of epoxy resin composition and anhydride hardener can depend in part on characteristic required in curable compositions to be generated or thermoset composition, required composition curing reaction and required composition working life.Herein, " working life " refer to that under application of temperature viscosity is increased to the times of the double of preparation initial viscosity or three times of costs.
At 25 DEG C, the viscosity of the composition epoxy resin prepared by the inventive method is generally within the scope of about 0.1Pa-s to about 500Pa-s.
for the method for curing composition
Curable epoxy preparation of the present invention or composition can solidify under the Conventional processing conditions forming thermosetting thing.The method manufacturing thermoset articles of the present invention can by execution such as gravitational casting, vacuum casting, automatic pressure gelling (APG), vacuum pressure gelling (VPG), injection, filament winding, lamination injection moulding (layupinjection), resin transfer moulding, pre-preg, dipping, coating, spraying, brushings.
Cured reaction condition comprises such as general within the scope of about 0 DEG C to about 300 DEG C; About 20 DEG C to about 250 DEG C in other embodiments; And about 50 DEG C are carried out described reaction at the temperature within the scope of about 200 DEG C in other embodiments.
The pressure of curing reaction can such as at about 0.01 bar to about 1000 bar; About 0.1 bar is to about 100 bar in other embodiments; And about 0.5 bar carries out under the pressure of about 10 bar in other embodiments.
Curable or the solidification of thermoset composition can such as can carry out the one period of scheduled time being enough to solidify described composition.For example, can select between about 1 minute to about 10 hours, in other embodiments, between about 2 minutes to about 5 hours, and in other embodiments, the set time between about 2.5 minutes to about 1 hour.
Curing of the present invention can be method in batches or continuously.Reactor for described method can be any reactor of knowing of those skilled in the art and utility appliance.
substrate
In one embodiment, curable compositions as described above can be dispensed on substrate and to be cured.Substrate is not limited by specific restriction.Therefore, substrate can comprise metal, such as stainless steel, iron, steel, copper, zinc, tin, aluminium etc.; The alloy of this metalloid and be coated with the thin slice of this metalloid and the laminated foil of this metalloid.Substrate can also comprise polymkeric substance, glass and various fiber, such as carbon/graphite; Boron; Quartz; Aluminum oxide; Glass, such as E glass, S glass, S-2 or C glass; And the silicon carbide fiber of silicon carbide or titaniferous.Commercially available fiber can comprise: organic fibre, such as, from Du Pont (DuPont) ; Salic fiber, such as, from 3M's fiber; Silicon carbide fiber, such as, from Japanese carbon (NipponCarbon) ; And the silicon carbide fiber of titaniferous, such as, from space portion (Ube) .In a particular embodiment, curable compositions can be used for forming carbon fiber composite, circuit card or printed circuit board (PCB) at least partially.In certain embodiments, substrate can be coated with expanding material to improve curable or curing composition soaking and/or clinging power substrate.
gained cured product characteristic
By solidifying solidification prepared by composition epoxy resin of the present invention or thermoset products should represent the workability of improvement and the balance of heat-mechanical characteristics (such as Procuring preparation viscosity, glass transition temperature, modulus and fracture toughness property).Combinationally use polyvalent alcohol and CSR with optimum level to provide and have compared with the snappiness of low viscosity, raising and elongation and the T of gained thermosetting thing gwithout harmful preparation reduced.Best polyvalent alcohol and CSR content have snappiness and the elongation of raising.
The T of thermoset products gby the solidifying agent that depends on for curable compositions and epoxy resin.In certain embodiments, the T of cured epoxy resin of the present invention git can be about 100 DEG C to about 300 DEG C; And more such as about 100 DEG C to about 265 DEG C.In certain embodiments, compared with not there is the analogous composition of CSR and/or the tough agent of polyvalent alcohol, the T of curing composition of the present invention greduction be less than 40 DEG C.
Similarly, the fracture toughness property of thermoset products is by the solidifying agent that depends on for curable compositions and epoxy resin.In general, the fracture toughness property of cured epoxy resin of the present invention can be about 0.4MPa/m 1/2to about 3MPa/m 1/2; And in other embodiments, about 0.6MPa/m 1/2to about 2MPa/m 1/2.In certain embodiments, compared with not there is the analogous composition of CSR and/or the tough agent of polyvalent alcohol, the fracture human nature percentage increase of curing composition of the present invention can in about 40 to about 200 scopes, and in other embodiments in about 40 to about 150 scopes.In one embodiment, elongation at break is greater than 9%.
end-use is applied
Composition epoxy resin of the present invention is applicable to prepare in foundry goods, coating, film, tackiness agent, veneer sheet, mixture (the clavate pipe of such as filament winding and can spiralization pipe, pultrusion, resin transfer moulding), the epoxy resin thermosetting thing of the form such as sealing agent, perfusion compound or cured product.In certain embodiments, it is generally preferred for processing the pultrusion of composition epoxy resin of the present invention, filament winding, casting, resin transfer moulding or vacuum impregnation.
As explanation of the present invention, in general, composition epoxy resin goes for casting, perfusion, sealing, molding and embossing.The present invention is particularly useful for the casting of all types electricity, perfusion and sealing applications; Mould and plastics embossing; And the composite parts manufactured based on epoxy resin, especially produce the large part based on epoxy resin produced by casting, perfusion and sealing.Gained matrix material goes for some application, such as electricity casting application or Electronic Packaging, foundry goods, mould, embedding, encapsulation, injection moulding, resin transfer moulding, mixture, coating etc.
example
Following instance and comparative example illustrate the present invention further in detail, but are not interpreted as and limit its scope.
Unless otherwise indicated, otherwise all chemical substances all purchased from Sigma-Aldrich (Sigma-Aldrich).D.E.R. tM383 (" DER383 "), PARALOID tMeXL2300G and PARALOID tMeXL2314CSR is commercially available from Dow Chemical.Voranol tM4000LM polyvalent alcohol is number molecular-weight average is 4000, commercially available poly-(propylene oxide) polyvalent alcohol from Tao Shi.Voranol tM4701 is can available from the polyether glycol of Tao Shi. 55-56 is the polyvalent alcohol available from Archie chemical company. 6320 is the polyvalent alcohol available from Bayer MaterialScience AG (BayerMaterialScience).
In the following example, use following analytical procedure: measure fracture toughness property according to ASTMD5045, measure glass transition temperature by dynamic mechanical analysis (DMA) and by ASTMD638 and D790 measurement mechanical characteristic.
example 1
By high-shear mechanical dispersion, 15gPARALOIDEXL2300G is distributed in 35.1gPolyG55-56.Then by the Speedmixer of Hao Xierde (Hauschild) tMcore shell rubbers dispersion liquid is made under 2200rpm, to mix 2 minutes with 133.6gD.E.R383,116.3g methyl tetrahydrophthalic anhydride and 3.0g1 Methylimidazole.Then mixture is positioned in vacuum chamber to remove any air retained.Once mixture is completely degassed, by its impouring mould to form the thick thin slice of 3.25mm.Mould is positioned in forced air convection baking oven immediately, and solidifies 2 hours at 90 DEG C, then solidify 4 hours at 150 DEG C, progressively cooled to room temperature subsequently.
After at room temperature adapting to about 2 weeks, then become by flaking suitable test sample book for measurement fracture toughness property and thermo-mechanical property.Report the test is in table 1.Sample only has 11.4% tension fracture elongation rate and 1.66MPa*m^0.5, its hint thermosetting thing be ductility and be suitable for flexible hose application.
comparative example A
By the Speedmixer of Hao Xierde tM160.3gD.E.R383 and 139.7g methyl tetrahydrophthalic anhydride and 3.0g1 Methylimidazole is made to mix 2 minutes with 2200rpm.Then mixture is positioned in vacuum chamber to remove any air retained.Once mixture is completely degassed, by its impouring mould to form the thick thin slice of 3.25mm.Mould is positioned in forced air convection baking oven immediately, and solidifies 2 hours at 90 DEG C, then solidify 4 hours at 150 DEG C, progressively cooled to room temperature subsequently.
After at room temperature adapting to about 2 weeks, then become by flaking suitable test sample book for measurement fracture toughness property and thermo-mechanical property.Report the test is in table 1.Sample only has 6% tension fracture elongation rate and 0.54MPa*m^0.5, its hint thermosetting thing be fragility and be unsuitable for flexible hose application.
comparative example B
By the Speedmixer of Hao Xierde tMmake 141.6gD.E.R383,123.3g methyl tetrahydrophthalic anhydride, 35.1gPolyG55-56 and 3.0g1 Methylimidazole mixes 2 minutes with 2200rpm.Then mixture is positioned in vacuum chamber to remove any air retained.Once mixture is completely degassed, by its impouring mould to form the thick thin slice of 3.25mm.Mould is positioned in forced air convection baking oven immediately, and solidifies 2 hours at 90 DEG C, then solidify 4 hours at 150 DEG C, progressively cooled to room temperature subsequently.
After at room temperature adapting to about 2 weeks, then become by flaking suitable test sample book for measurement fracture toughness property and thermo-mechanical property.Report the test is in table 1.Sample only has 8.5% tension fracture elongation rate and 0.90MPa*m^0.5.Although observe that elongation and fracture toughness property improve a little, composition fails the minimum requirements of satisfied 8.0% elongation at break.
comparative example C
25.9gPARALOIDEXL2300G mechanical dispersion is formed uniform dispersion in 146.6gDER383.Then by the Speedmixer of Hao Xierde tMmixture is made under 2200rpm, to mix 2 minutes with 127.6g methyl tetrahydrophthalic anhydride and 3.0g1 Methylimidazole.Then mixture is positioned in vacuum chamber to remove any air retained.Once mixture is completely degassed, by its impouring mould to form the thick thin slice of 3.25mm.Mould is positioned in forced air convection baking oven immediately, and solidifies 2 hours at 90 DEG C, then solidify 4 hours at 150 DEG C, progressively cooled to room temperature subsequently.
After at room temperature adapting to about 2 weeks, then become by flaking suitable test sample book for measurement fracture toughness property and thermo-mechanical property.Report the test is in table 1.Sample only has 5.4% tension fracture elongation rate and 1.89MPa*m^0.5.Although observe that elongation and fracture toughness property significantly improve, composition fails the minimum requirements of satisfied 8.0% elongation at break.
example 2
By high-shear mechanical dispersion, 22.5gPARALOIDEXL2314 is distributed in 67.5gVoranol4701.Then by the Speedmixer of Hao Xierde tMcore shell rubbers dispersion liquid is made under 2200rpm, to mix 2 minutes with 112.2gD.E.R383 and 97.8g methyl tetrahydrophthalic anhydride and 3.0g1 Methylimidazole.Then mixture is positioned in vacuum chamber to remove any air retained.Once mixture is completely degassed, by its impouring mould to form the thick thin slice of 3.25mm.Mould is positioned in forced air convection baking oven immediately, and solidifies 2 hours at 90 DEG C, then solidify 4 hours at 150 DEG C, progressively cooled to room temperature subsequently.
After at room temperature adapting to about 2 weeks, then become by flaking suitable test sample book for measurement fracture toughness property and thermo-mechanical property.Report the test is in table 1.Sample only has 21.8% tension fracture elongation rate and 1.14MPa*m^0.5, its hint thermosetting thing be ductility and be suitable for flexible hose application.
comparative example D
By the Speedmixer of Hao Xierde tMmake 124.3gD.E.R383,108.2g methyl tetrahydrophthalic anhydride, 67.5gVoranol4701 and 3.0g1-Methylimidazole mixes 2 minutes with 2200rpm.Then mixture is positioned in vacuum chamber to remove any air retained.Once mixture is completely degassed, by its impouring mould to form the thick thin slice of 3.25mm.Mould is positioned in forced air convection baking oven immediately, and solidifies 2 hours at 90 DEG C, then solidify 4 hours at 150 DEG C, progressively cooled to room temperature subsequently.
After at room temperature adapting to about 2 weeks, then become by flaking suitable test sample book for measurement fracture toughness property and thermo-mechanical property.Report the test is in table 1.Sample only has 6.6% tension fracture elongation rate and 0.80MPa*m^0.5.Although observe that elongation and fracture toughness property improve a little, composition fails the minimum requirements of satisfied 9.0% elongation at break.
example 3
By high-shear mechanical dispersion, 22.5gPARALOIDEXL2314 is distributed in 67.5gAcclaim6320.Then by the Speedmixer of Hao Xierde tMcore shell rubbers dispersion liquid is made under 2200rpm, to mix 2 minutes with 112.2gD.E.R383 and 97.8g methyl tetrahydrophthalic anhydride and 3.0g1-Methylimidazole.Then mixture is positioned in vacuum chamber to remove any air retained.Once mixture is completely degassed, by its impouring mould to form the thick thin slice of 3.25mm.Mould is positioned in forced air convection baking oven immediately, and solidifies 2 hours at 90 DEG C, then solidify 4 hours at 150 DEG C, progressively cooled to room temperature subsequently.
After at room temperature adapting to about 2 weeks, then become by flaking suitable test sample book for measurement fracture toughness property and thermo-mechanical property.Report the test is in table 1.Sample only has 20.2% tension fracture elongation rate and 1.12MPa*m^0.5, its hint thermosetting thing be ductility and be suitable for flexible hose application.
example 4
22.8gPARALOIDEXL2300G mechanical dispersion is formed uniform dispersion in 129.0gDER383.Then by the Speedmixer of Hao Xierde tMmixture is made under 2200rpm, to mix 2 minutes with 112.3g methyl tetrahydrophthalic anhydride, 36gPolyG55-56 and 3.0g1-Methylimidazole.Then mixture is positioned in vacuum chamber to remove any air retained.Once mixture is completely degassed, by its impouring mould to form the thick thin slice of 3.25mm.Mould is positioned in forced air convection baking oven immediately, and solidifies 7 minutes at 93 DEG C, solidify 7 minutes at 107 DEG C, solidify 7 minutes at 118 DEG C, solidify 9 minutes at 127 DEG C, and solidify 9 minutes at 135 DEG C, progressively cooled to room temperature subsequently.
After at room temperature adapting to about 2 weeks, then become by flaking suitable test sample book for measurement fracture toughness property and thermo-mechanical property.Report the test is in table 1.Sample only has 16.1% tension fracture elongation rate and 2.2MPa*m^0.5.
example 5
22.8gPARALOIDEXL2300G mechanical dispersion is formed uniform dispersion in 129.0gDER383.Then by the Speedmixer of Hao Xierde tMmixture is made under 2200rpm, to mix 2 minutes with 112.3g methyl tetrahydrophthalic anhydride, 36gVoranol4701 and 3.0g-Methylimidazole.Then mixture is positioned in vacuum chamber to remove any air retained.Once mixture is completely degassed, by its impouring mould to form the thick thin slice of 3.25mm.Mould is positioned in forced air convection baking oven immediately, and solidifies 7 minutes at 93 DEG C, solidify 7 minutes at 107 DEG C, solidify 7 minutes at 118 DEG C, solidify 9 minutes at 127 DEG C, and solidify 9 minutes at 135 DEG C, progressively cooled to room temperature subsequently.
After at room temperature adapting to about 2 weeks, then become by flaking suitable test sample book for measurement fracture toughness property and thermo-mechanical property.Report the test is in table 1.Sample only has 14.6% tension fracture elongation rate and 1.6MPa*m^0.5.
example 6
22.8gPARALOIDEXL2300G mechanical dispersion is formed uniform dispersion in 129.0gDER383.Then by the Speedmixer of Hao Xierde tMmixture is made under 2200rpm, to mix 2 minutes with 112.3g methyl tetrahydrophthalic anhydride, 36gVoranolP4000 and 3.0g1-Methylimidazole.Then mixture is positioned in vacuum chamber to remove any air retained.Once mixture is completely degassed, by its impouring mould to form the thick thin slice of 3.25mm.Mould is positioned in forced air convection baking oven immediately, and solidifies 7 minutes at 93 DEG C, solidify 7 minutes at 107 DEG C, solidify 7 minutes at 118 DEG C, solidify 9 minutes at 127 DEG C, and solidify 9 minutes at 135 DEG C, progressively cooled to room temperature subsequently.
After at room temperature adapting to about 2 weeks, then become by flaking suitable test sample book for measurement fracture toughness property and thermo-mechanical property.Report the test is in table 1.Sample only has 10.5% tension fracture elongation rate and 1.7MPa*m^0.5.
Table 1

Claims (15)

1. a curable resin composition, comprises:
A) epoxy resin;
B) anhydride hardener;
C) polyvalent alcohol;
D) core shell rubbers, and
E) catalyzer.
2. curable resin composition according to claim 1, wherein said curable resin composition is by being scattered in described core shell rubbers to form dispersion liquid in described epoxy resin, and mixes prepared by described dispersion liquid and described stiffening agent, described catalyzer and described polyol component.
3. the curable resin composition according to any one of claim 1 or 2, wherein said curable resin composition is by being scattered in described core shell rubbers to form dispersion liquid in described anhydride hardener, and mixes prepared by described dispersion liquid and described epoxy resin, described catalyzer and described polyol component.
4. the curable resin composition according to any one of Claim 1-3, wherein said curable resin composition is by being scattered in described core shell rubbers to form dispersion liquid in described polyol component, and mixes prepared by described dispersion liquid and described epoxy resin, described catalyzer and described stiffening agent.
5. the curable resin composition according to any one of claim 1 to 4, wherein by the total weight of described curable resin composition, described epoxy resin exists with the amount in 10 % by weight to 90 % by weight scopes, described anhydride hardener exists with the amount in 10 % by weight to 90 % by weight scopes, described polyvalent alcohol exists with the amount in 1 % by weight to 30 % by weight scope, described core shell rubbers exists with the amount in 1 % by weight to 25 % by weight scope, and described catalyzer exists with the amount in 0.1 % by weight to 10 % by weight scope.
6. the curable resin composition according to any one of claim 1 to 5, wherein said anhydride hardener is selected from by aromatic series and cyclic aliphatic acid anhydride and its group formed.
7. curable resin composition according to claim 6, wherein said anhydride hardener is methylnadic anhydride (nadic-methyl-anhydride) or methyl tetrahydrophthalic anhydride.
8. the curable resin composition according to any one of claim 1 to 7, wherein said polyol component is selected from by polyether glycol, polyester polyol, polycarbonate polyol and its group formed.
9. curable resin composition according to claim 8, wherein said polyol component is selected from by the following group formed: derived from the polyether glycol of ethylene oxide, propylene oxide, oxybutylene, tetrahydrofuran (THF) or its mixture; Derived from succinic acid, pentanedioic acid, hexanodioic acid, Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid or its mixture and ethylene glycol, 1,2-propylene glycol, 1, the polyester polyol of 4-butyleneglycol, 1,6-hexylene glycol, neopentyl glycol, Diethylene Glycol, glycerol, TriMethylolPropane(TMP) or its mixture copolymerization; Caprolactone-derived polyester polyol; Derived from the polycarbonate polyol of ethylene glycol, 1,2-PD, BDO, 1,6-hexylene glycol, neopentyl glycol, Diethylene Glycol, glycerol, TriMethylolPropane(TMP) or its mixture and the copolymerization of carbonic ether precursor; And the mixture of its two or more polyvalent alcohol any.
10. the curable resin composition according to any one of claim 1 to 9, wherein said polyol component comprises molecular-weight average and is 2000 to 12000 and average functionality is the polyvalent alcohol of 1.5 to 6.0.
11. curable resin compositions according to any one of claim 1 to 10, wherein said catalyzer be selected from by imidazoles, the imidazoles be substituted, quaternary ammonium salt, chromium cpd with and composition thereof the group that forms.
12. 1 kinds, for the preparation of the method for curable resin composition, comprise:
A (), with high-shear mixer, in discrete areas, under the dispersion condition forming core shell rubbers dispersion liquid, makes core shell rubbers be scattered in and is selected from the component of the group be made up of polyol component, hardener component and epoxy resin ingredient; And (b) makes described core shell rubbers dispersion liquid be mixed into i) catalyzer and ii) comprise in the epoxy preparation product of at least one in epoxy resin, anhydride hardener and polyvalent alcohol, thus form described curable resin composition.
13. 1 kinds of curable resin compositions, comprise:
A) epoxy resin;
B) anhydride hardener;
C) be selected from by polyether polyol, polyester polyol, polycaprolactone polyol, hydroxy-end capped polyhutadiene with and composition thereof the polyol component of group that forms; And
D) core shell rubbers, it comprises rubber particles core and outer shell, and the particle diameter of wherein said core shell rubbers is 0.01 μm to 0.5 μm.
14. curable resin compositions according to claim 13, its elongation at break is greater than 9%.
15. 1 kinds of article be made up of curable resin composition according to claim 13, described article are selected from the group be made up of mixture, coating, veneer sheet and tackiness agent.
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